JP4937703B2 - Method for producing polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polymer, capable of reducing the amount of a colored substance formed in the production or after the production of the polymer having amino groups to produce the polymer having a good color. <P>SOLUTION: This method for producing the polymer is provided by polymerizing a monomer components containing the following monomer (A) and monomer (B) and neutralizing a part of the monomer (A) before the polymerization reaction or in the polymerization reaction with an organic acid without containing an aromatic ring. The fiber surface-modifying polymer obtained by the method is also provided. Provided that, (A) an unsaturated bond-containing monomer having at least 1 kind of an amino group selected from primary to tertiary amino groups, (B) an unsaturated bond-containing monomer having a hydrophobic group, and without having the primary to tertiary amino groups. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a method for producing an amine-based polymer with reduced coloring substances, and a fiber surface modifying polymer obtained by the method.

A polymer having an amino group is a polymer used in a wide range of fields. For example, it is used for surface modifiers such as fibers by utilizing the high adsorptivity of amino groups to the surface of the substance (Patent Documents 1 and 2). Such polymers and their solutions generally tend to be colored because they tend to produce colored substances during or after production. Coloring is not only unfavorable in appearance, but also causes contamination of the surface of substances (fibers, etc.) in the system during use.
JP 2005-314843 A JP 7-316590 A

  An object of the present invention is to provide a method for producing a polymer having a good hue by reducing the amount of a coloring substance produced during or after the production of a polymer having an amino group.

The present invention is a method for producing a polymer by polymerizing monomer components containing the following monomer (A) and monomer (B), wherein a part or all of the monomer (A) is removed before or during the polymerization reaction. Provided is a method for producing a polymer, which is neutralized with an organic acid containing no aromatic ring, and a fiber surface modifying polymer obtained by this production method.
(A) an unsaturated bond-containing monomer having at least one amino group selected from primary to tertiary amino groups (B) an unsaturated bond containing a hydrophobic group and not having primary to tertiary amino groups monomer

  According to the production method of the present invention, it is possible to reduce the amount of a coloring substance produced during or after production of a polymer having an amino group and obtain a polymer having a good hue. Further, the polymer obtained by the present invention can modify the fiber surface without contaminating the fiber surface.

[Monomer component]
The monomer component used in the present invention includes monomer (A) and monomer (B). The monomer (A) is an unsaturated bond-containing monomer having at least one amino group selected from primary to tertiary amino groups.

  Examples of the monomer (A) include amino group-containing (meth) acrylic acid esters, (meth) acrylamides, styrenes, and diallyl compounds. Here, “(meth) acryl” means acrylic or methacrylic.

  Specific examples include monomers represented by general formulas (I) to (III).

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ are the same or different and represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, or An alkenyl group or a benzyl group, X represents an —O— or —NH— group, and Y represents a linear or branched alkylene group having 1 to 4 carbon atoms.

(In the formula, R ¹ , R ² , R ³ and Y are as defined above. N represents 0 or 1.)

(In the formula, R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom or a methyl group, and R ⁶ represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, or Represents an alkenyl group or a benzyl group.)
Examples of the monomer represented by the general formula (I) include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, dibutylaminoethyl (meth) ) Acrylate, diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropylaminopropyl ( (Meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butylaminopropyl ( Data) with a dialkylamino group such as acrylamide (meth) acrylic acid ester or (meth) acrylamide.

  Examples of the monomer represented by the general formula (II) include styrenes having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene. Examples of the monomer represented by the general formula (III) include diallylamine compounds such as diallylmethylamine and diallylamine.

  The monomer (B) of the present invention is an unsaturated bond-containing monomer having a hydrophobic group and not having a primary to tertiary amino group. Examples of the hydrophobic group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

  As the monomer (B), a (meth) acrylic acid ester having 1 to 22 carbon atoms, preferably 4 to 22 linear, branched or cyclic alkyl group, alkenyl group, or aryl group, (meth) There may be mentioned at least one selected from acrylamide, vinyl ester, vinyl ether and styrenes.

  Specific examples of the monomer (B) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, oleyl (meth) acrylate, etc. (Meth) acrylic acid ester having a linear, branched or cyclic alkyl group or alkenyl group having 1 to 22 carbon atoms; (meth) acrylic acid having an arylalkyl group such as benzyl (meth) acrylate Steal; methyl (meth) acrylamide, ethyl (meth) acrylamide, isopropyl (meth) acrylamide, butyl (meth) acrylamide, t-butyl (meth) acrylamide, cyclohexyl (meth) acrylamide, 2-ethylhexyl (meth) acrylamide, lauryl ( C1-C22 linear, branched or cyclic alkyl or alkenyl groups such as meth) acrylamide, stearyl (meth) acrylamide, behenyl (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, etc. (Meth) acrylamide having an arylalkyl group such as benzyl (meth) acrylamide; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, Vinyl esters having a linear, branched or cyclic alkyl group or alkenyl group having 1 to 22 carbon atoms, such as vinyl titanate, vinyl decanoate, vinyl laurate, vinyl palmitate, vinyl stearate; methyl vinyl ether; Examples include vinyl ethers such as ethyl vinyl ether and butyl vinyl ether; styrenes such as styrene, α-methyl styrene, methyl styrene, butyl styrene, t-butyl styrene, and dimethyl styrene.

  In the method of the present invention, the monomer (A) and the monomer (B) are used in a weight ratio of (A) / (B) = 20/80 to 98/2 from the viewpoint of use as a fiber surface modifying polymer. Is preferred.

  One or more types of monomer (A) and monomer (B) can be used. In addition to monomer (A) and monomer (B), an unsaturated bond-containing monomer (hereinafter referred to as monomer (C)) copolymerizable with monomer (A) and monomer (B) may be copolymerized.

  As monomer (C), for example, vinyl alcohol; (meth) acrylic acid ester or (meth) acrylamide having a hydroxyalkyl group having 1 to 22 carbon atoms such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylamide; Polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, lauroxy polyethylene glycol (meth) acrylate (degree of polymerization of ethylene glycol 1 to 100), polypropylene glycol (meth) acrylate (degree of polymerization of propylene glycol 1 to 1) 50), polyalkylene (carbon number of alkylene group: 1 to 8; linear or branched) oxy such as polybutylene glycol (meth) acrylate (the degree of polymerization of butylene glycol is 1 to 50) (Meth) acrylic acid ester having a chain; (meth) acrylic acid ester of polyhydric alcohol such as glycerin (meth) acrylate; acrylamide; diacetone (meth) acrylamide; N-vinyl cyclic amide such as N-vinylpyrrolidone; (Meth) acryloylmorpholine; vinyl chloride; acrylonitrile; (meth) acrylic acid, maleic acid, itaconic acid, vinyl compounds having a carboxyl group such as styrenecarboxylic acid; 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid And vinyl compounds having a sulfonic acid group such as

  The copolymerization amount of these monomers (C) is preferably 0 to 80% by weight based on the total amount of monomers from the viewpoint of use as a fiber surface modifying polymer.

[Organic acid containing no aromatic ring]
The organic acid that does not contain an aromatic ring used in the present invention means that the number of electrons contained in the π-electron system on the ring satisfies 4n + 2 (n = 1, 2, 3,...) (Huckel rule). An organic acid having no saturated ring structure (so-called aromaticity). When an organic acid containing an aromatic ring is used, the amount of the coloring substance cannot be reduced so much or may be increased.

  Organic acids that do not contain aromatic rings include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid. Saturated carboxylic acid having 1 to 22 carbon atoms such as acid; unsaturated carboxylic acid having 1 to 22 carbon atoms such as allyl carboxylic acid, undecylenic acid, oleic acid, linoleic acid, α-linolenic acid; oxalic acid, malonic acid , Succinic acid, glutaric acid, adipic acid, sebacic acid, decanedicarboxylic acid, fumaric acid, maleic acid and other polyvalent carboxylic acids having 1 to 22 carbon atoms; glycolic acid, lactic acid, tartaric acid, malic acid, citric acid, glucone Hydroxycarboxylic acid having 1 to 22 carbon atoms such as acid; Organic sulfonic acid having 1 to 22 carbon atoms such as methanesulfonic acid and N-methyltaurine; Lauryl The total sulfuric acid esters having a carbon number of 1 to 22 such as an acid, and the like. In this invention, 1 or more types of these organic acids which do not contain an aromatic ring can be used.

  Among these, it is preferable to use a carboxylic acid having 1 to 22 carbon atoms, such as a saturated carboxylic acid, an unsaturated carboxylic acid, a polyvalent carboxylic acid, and a hydroxycarboxylic acid, which does not contain the aromatic ring. A hydroxycarboxylic acid of ˜22 is more preferred.

[Method for producing polymer]
In the method of the present invention, a part or all of the monomer (A) is neutralized with an organic acid not containing an aromatic ring before or during the polymerization reaction of the monomer component.

  Here, “before polymerization reaction” refers to a period before a monomer having a predetermined reaction temperature comes into contact with an initiator. Here, the predetermined reaction temperature refers to a temperature at which the initiator substantially starts the polymerization reaction. Therefore, the state before the predetermined reaction temperature after the contact of the monomer and the initiator is included in “before the polymerization reaction”. Further, a state where the monomer has reached the predetermined reaction temperature and is not in contact with the initiator is included in “before the polymerization reaction”.

  “During polymerization reaction” means a period from when a monomer having a predetermined reaction temperature comes into contact with an initiator until the addition of the initiator to the reaction mixture is completed. In the period until the addition of the initiator is completed, the period in which both the monomer and the initiator are added simultaneously, the period in which only the initiator is added, the period in which only the monomer is added, or neither the initiator and the monomer are added There is no problem even if there is a period.

  It is particularly preferable to neutralize with an organic acid not containing an aromatic ring before the polymerization reaction from the viewpoint of reducing the amount of the colored substance. In addition, for the purpose of improving the polymerization reaction rate, a period in which only the initiator is added may be set after the period in which both the monomer and the initiator are simultaneously added. In that case, only the initiator is added. It is preferable to neutralize with an organic acid that does not contain an aromatic ring before the period or at the beginning of the period in which only the initiator is added.

  0.1-1.5 equivalent is preferable with respect to the amino group of a monomer (A), and, as for the usage-amount of the organic acid which does not contain an aromatic ring, 0.2-1.2 equivalent is more preferable, and 0.3-1 0.0 equivalents are particularly preferred.

  The amount of the coloring substance in the polymer varies greatly depending on the composition of the polymer, the polymerization solvent, etc., and the optimal organic acid and the amount of use thereof vary, but does not contain an aromatic ring before or during the polymerization reaction. When neutralized with an organic acid, the amount of the coloring substance can be significantly reduced as compared with a case where neutralization with an organic acid containing an aromatic ring, neutralization after a polymerization reaction, or no neutralization at all.

  In the method of the present invention, the monomer component is preferably radically polymerized by a solution polymerization method or a suspension polymerization method.

  As the radical polymerization initiator used in the present invention, a general radical polymerization initiator can be used. For example, peroxide initiators such as lauroyl peroxide, benzoyl peroxide, ammonium persulfate; -Azo initiators such as azobis (2,4-dimethylvaleronitrile) and 2,2'-azobisisobutyronitrile. The amount of the radical polymerization initiator used varies depending on the type and concentration of the monomer, the type of the initiator, the reaction temperature, etc., but is usually preferably 0.1 to 10 mol% with respect to the total amount of monomers, 0.5 to 8 Mole% is more preferable.

  The method for producing the polymer of the present invention can be carried out by an ordinary general solution polymerization method, suspension polymerization method or the like, and is not particularly limited, but specifically, the following production methods are exemplified. .

  First, the reaction vessel is heated to a predetermined temperature. The temperature in the reaction vessel at that time can be freely set according to the type and amount of the radical polymerization initiator, the type of solvent, the type and concentration of the monomer, etc., but the half-life of the radical polymerization initiator is 200 minutes or less. It is preferable in terms of reaction control that the Usually, the temperature is about 40 to 120 ° C, preferably 50 to 100 ° C. In addition, an appropriate amount of a solvent or a solvent and other components (monomer, etc.) may be added in advance to the reaction vessel. If necessary, oxygen in the reaction vessel may be distilled off by replacement with an inert gas such as nitrogen.

  Next, the monomer and the radical polymerization initiator are continuously or intermittently dropped into the reaction vessel. At this time, a monomer or a radical polymerization initiator may be dropped in a solvent. The concentration of the monomer and radical polymerization initiator at that time is preferably 20 to 100% by weight in the case of a normal monomer, and preferably 1 to 100% by weight in the case of a radical polymerization initiator. Moreover, each monomer, radical polymerization initiator, or a solution thereof may be dropped into the reaction vessel separately, or mixed and dropped. When dropping separately, the dropping timing and speed may be shifted. Each dropping may be performed continuously or intermittently. These dripping liquids may distill off the dissolved oxygen in the liquid by replacement with an inert gas such as nitrogen, if necessary. The dropping time can be freely set according to the type and concentration of the monomer, the type and amount of the radical polymerization initiator, the type of solvent, the reaction temperature, etc., but the reaction rate of all monomers immediately after the completion of dropping of all monomers is 50 to 50%. 100% is preferable in terms of reaction control. The time is usually about 1 to 20 hours. Moreover, the temperature in the reaction container during dripping can be suitably changed within the said temperature range.

  The method for adding an organic acid not containing an aromatic ring is as follows: (i) a method in which a monomer and / or initiator is added in advance to a reaction vessel, and (ii) a monomer solution before being dropped into the reaction vessel. Examples include a method of adding in advance, (iii) a method of dropping an organic acid or a solution thereof into a reaction vessel to which a monomer and / or initiator are added, but is not particularly limited. You may combine.

  In order to complete the polymerization reaction after completion of the dropping, the reaction solution is preferably maintained for a certain time within the above temperature range. The holding time is about 0 to 15 hours.

  The solvent used in the method of the present invention is not particularly limited, and water; alcohol solvents such as methanol, ethanol and isopropanol; aromatic solvents such as 2-phenoxyethanol and phenyltriglycol may be used alone or in appropriate combination. it can.

[Polymer and its use]
The weight average molecular weight (Mw) of the polymer obtained by the method of the present invention is not particularly limited, but is preferably 2,000 or more from the viewpoint of use as a fiber surface modifying polymer.

  In addition, Mw of the polymer of this invention uses the value by a gel permeation chromatography (GPC) measurement. As an eluent, any one of water, alcohol, chloroform, dimethylformamide, tetrahydrofuran, acetonitrile and a combination of these solvents is used, and the molecular weight is converted to polyethylene oxide or polystyrene.

  The polymer obtained by the method of the present invention has a good hue and can be used for various applications. However, it is preferably used as a fiber surface modifying polymer, and particularly a detergent or a fiber treatment agent in which coloring is a problem. It is useful as a polymer added to.

  In the following examples, the hue of the polymer solution was measured by the following method.

<Evaluation method of hue>
Using a spectroscopic color difference meter (SE2000; manufactured by Nippon Denshoku Industries Co., Ltd.), the APHA value (0 to 500; the larger the value, the larger the color) of the polymer solution was measured.

[Example 1] (neutralization before reaction)
A glass separable flask having an internal volume of 1 L was sufficiently purged with nitrogen. Thereto, 54.7 g of 95% ethanol (hereinafter abbreviated as ethanol) was added as a solvent, and the mixture was heated and held with stirring until the internal temperature reached 78 to 80 ° C. In another container, 206.97 g of dimethylaminoethyl methacrylate, 83.73 g of lauryl methacrylate, and 130.1 g of ethanol were uniformly mixed as monomers. While maintaining the liquid temperature at 40 ° C. or lower, 67.00 g of DL-lactic acid (85-92% aqueous solution; manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to the mixed solution for neutralization. Then, 4.09 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65B; manufactured by Wako Pure Chemical Industries, Ltd.) as an initiator was dissolved in the obtained solution to prepare a monomer / An initiator solution was obtained.

  The monomer / initiator solution was dropped into the flask at a constant rate over 3 hours. After completion of dropping of the monomer / initiator solution, a solution (initiator solution) prepared by dissolving 10.22 g of initiator V-65B in 40.9 g of ethanol was dropped into the flask at a constant rate over 5 hours. After completion of the dropwise addition of the initiator solution, a polymer ethanol solution was obtained by maintaining at around 80 ° C. for 2 hours.

The weight average molecular weight (Mw) of this polymer (water / ethanol = 7/3 system, polyethylene oxide equivalent) was 7300. The composition of this polymer analyzed by ¹ H-NMR was the same as the charged monomer composition.

[Example 2] (neutralization during reaction)
A glass separable flask having an internal volume of 1 L was sufficiently purged with nitrogen. Ethanol 48.0g was added there, and it heated and maintained until internal temperature became 78-80 degreeC, stirring. In another container, 206.97 g of dimethylaminoethyl methacrylate, 83.73 g of lauryl methacrylate, and 136.8 g of ethanol were uniformly mixed as monomers. Into the resulting solution, 4.09 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65B; manufactured by Wako Pure Chemical Industries, Ltd.) as an initiator was dissolved to give a monomer / initiator. A solution was obtained (no neutralization was performed).

  The monomer / initiator solution was dropped into the flask at a constant rate over 3 hours. After completion of the dropwise addition of the monomer / initiator solution, 67.00 g of DL-lactic acid (85-92% aqueous solution; manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise at a constant rate over 2 hours. Next, immediately after DL-lactic acid was dropped into the flask, a solution (initiator solution) in which 10.22 g of initiator V-65B was dissolved in 40.9 g of ethanol was added to the flask at a constant rate over 5 hours. It was dripped. After completion of the dropwise addition of the initiator solution, an ethanol solution of the polymer was obtained by holding at around 80 ° C. for 1 hour.

The Mw (water / ethanol = 7/3 system, converted to polyethylene oxide) of this polymer was 10900. The composition of this polymer analyzed by ¹ H-NMR was the same as the charged monomer composition.

[Comparative Example 1] (Neutralized after reaction)
A glass separable flask having an internal volume of 1 L was sufficiently purged with nitrogen. Ethanol 53.9g was added there, and it heated and maintained until the internal temperature became 78-80 degreeC, stirring. In a separate container, 249.19 g of dimethylaminoethyl methacrylate, 100.81 g of lauryl methacrylate, and 130.1 g of ethanol were uniformly mixed as monomers. Into the resulting solution, 4.09 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65B; manufactured by Wako Pure Chemical Industries, Ltd.) as an initiator was dissolved to give a monomer / initiator. A solution was obtained (no neutralization was performed).

  The monomer / initiator solution was dropped into the flask at a constant rate over 3 hours. After completion of dropping of the monomer / initiator solution, a solution (initiator solution) obtained by dissolving 12.30 g of initiator V-65B in 49.2 g of ethanol was dropped into the flask at a constant rate over 5 hours. After completion of the dropping of the initiator solution, the mixture was kept at around 80 ° C. for 2 hours, and then 80.67 g of DL-lactic acid was added to obtain a polymer ethanol solution.

Mw (water / ethanol = 7/3 system, polyethylene oxide equivalent) of this polymer was 10200. The composition of this polymer analyzed by ¹ H-NMR was the same as the charged monomer composition.

  Table 1 summarizes the polymer compositions and neutralization conditions of Examples 1 and 2 and Comparative Example 1 and the hue of the polymer solution.

Example 3 (neutralization before reaction)
In Example 1, 82.8 g of 2-phenoxyethanol (phenylglycol (PhG); manufactured by Nippon Emulsifier Co., Ltd.) was used instead of ethanol added to the separable flask as a solvent, and dimethylaminoethyl in the monomer / initiator solution was used. The amount of methacrylate was changed to 165.58 g, the amount of lauryl methacrylate was changed to 6699 g, PhG was changed to 301.6 g instead of ethanol, the amount of DL-lactic acid was changed to 53.60 g, and the amount of V-65B was changed to 3.27 g. Further, the amount of V-65B in the initiator solution dropped after the completion of dropping of the monomer / initiator solution was changed to 3.27 g, and PhG was changed to 29.4 g instead of ethanol. Other than that was carried out similarly to Example 1, and obtained the polymer PhG solution.

The Mw (water / ethanol = 7/3 system, polyethylene oxide equivalent) of this polymer was 6100. The composition of this polymer analyzed by ¹ H-NMR was the same as the charged monomer composition.

[Comparative Example 2] (Neutralized after reaction)
In Example 3, the amount of PhG added to the separable flask was changed to 84.0 g, the amount of dimethylaminoethyl methacrylate in the monomer / initiator solution was 199.35 g, the amount of lauryl methacrylate was 80.65 g, and the amount of PhG was 300. The amount of V-65B in the initiator solution dropped after the completion of dropping of the monomer / initiator solution was changed to 3.94 g, and the amount of PhG was changed to 35.4 g. Furthermore, DL-lactic acid was not added to the monomer / initiator solution, but was finally held at around 80 ° C. for 2 hours, and then 64.53 g was added. Otherwise in the same manner as in Example 3, a polymer PhG solution was obtained. Mw (water / ethanol = 7/3 system, polyethylene oxide equivalent) of this polymer was 8,500. The composition of this polymer analyzed by ¹ H-NMR was the same as the charged monomer composition.

  Table 2 summarizes the polymer compositions and neutralization conditions of Example 3 and Comparative Example 2 and the hues of the polymer solutions.

Example 4 (neutralization before reaction)
In Example 3, a polymer PhG-30 solution was obtained in the same manner as in Example 3 except that the solvent used was changed to phenyltriglycol (PhG-30; manufactured by Nippon Emulsifier Co., Ltd.) instead of PhG. The Mw (water / ethanol = 7/3 system, polyethylene oxide equivalent) of this polymer was 6600. The composition of this polymer analyzed by ¹ H-NMR was the same as the charged monomer composition.

Example 5 (neutralization before reaction)
In Example 4, the amount of PhG-30 added to the separable flask was 83.2 g, the amount of dimethylaminoethyl methacrylate in the monomer / initiator solution was 177.61 g, the amount of lauryl methacrylate was 71.86 g, and the amount of PhG-30 was 301.3 g, DL-lactic acid amount was changed to 34.50 g, V-65B amount was changed to 5.26 g, and the amount of V-65B in the initiator solution dropped after completion of dropping of the monomer / initiator solution was 3.51 g, The amount of PhG-30 was changed to 31.6 g. Otherwise in the same manner as in Example 4, a polymer PhG-30 solution was obtained. The Mw (water / ethanol = 7/3 system, polyethylene oxide equivalent) of this polymer was 7200. The composition of this polymer analyzed by ¹ H-NMR was the same as the charged monomer composition.

Example 6 (neutralization before reaction)
In Example 4, the amount of PhG-30 added to the separable flask was 80.5 g, the amount of dimethylaminoethyl methacrylate in the monomer / initiator solution was 170.06 g, the amount of lauryl methacrylate was 68.80 g, and the amount of PhG-30 was 291.7 g, in place of DL-lactic acid, glycolic acid (about 70% aqueous solution; manufactured by Wako Pure Chemical Industries, Ltd.) was changed to 58.76 g, and the amount of V-65B was changed to 5.04 g, and the monomer / initiator solution The amount of V-65B in the initiator solution dropped after the completion of dropping was changed to 3.36 g and the amount of PhG-30 was changed to 30.2 g. Otherwise in the same manner as in Example 4, a polymer PhG-30 solution was obtained. The Mw (water / ethanol = 7/3 system, polyethylene oxide equivalent) of this polymer was 8,600. The composition of this polymer analyzed by ¹ H-NMR was the same as the charged monomer composition.

[Comparative Example 3] (Neutralized after reaction)
In Comparative Example 2, a polymer PhG-30 solution was obtained in the same manner as in Comparative Example 2 except that the solvent used was changed to PhG-30 instead of PhG. The Mw (water / ethanol = 7/3 system, polyethylene oxide equivalent) of this polymer was 11000. The composition of this polymer analyzed by ¹ H-NMR was the same as the charged monomer composition.

[Comparative Example 4] (neutralized with organic acid containing aromatic ring before reaction)
In Example 4, the amount of PhG-30 added to the separable flask was 82.9 g, the amount of dimethylaminoethyl methacrylate in the monomer / initiator solution was 161.55 g, the amount of lauryl methacrylate was 65.36 g, and the amount of PhG-30 was 302.8 g, p-toluenesulfonic acid instead of DL-lactic acid was changed to 58.67 g, V-65B amount was changed to 4.79 g, and V- in the initiator solution dropped after completion of dropping of the monomer / initiator solution. The amount of 65B was changed to 3.19 g, and the amount of PhG-30 was changed to 28.7 g. Otherwise in the same manner as in Example 4, a polymer PhG-30 solution was obtained. The Mw (water / ethanol = 7/3 system, polyethylene oxide equivalent) of this polymer was 10700. The composition of this polymer analyzed by ¹ H-NMR was the same as the charged monomer composition.

  Table 3 summarizes the polymer compositions and neutralization conditions of Examples 4 to 6 and Comparative Examples 3 and 4, and the hues of the polymer solutions.

Example 7 (neutralization before reaction)
In Example 4, 73.9 g of PhG-30 added to the separable flask, 149.33 g of dimethylaminoethyl methacrylate in the monomer / initiator solution, 57.89 g of butyl methacrylate instead of lauryl methacrylate, PhG -Change 30 amount to 259.2g, DL-lactic acid amount to 48.34g, V-65B amount to 2.70g, and add V-65B amount in initiator solution to be dropped after completion of dropping of monomer / initiator solution. The amount of PhG-30 was changed to 4.04 g and 36.4 g. Otherwise in the same manner as in Example 4, a polymer PhG-30 solution was obtained. Mw (water / ethanol = 7/3 system, polyethylene oxide equivalent) of this polymer was 12,800. The composition of this polymer analyzed by ¹ H-NMR was the same as the charged monomer composition.

[Comparative Example 5] (Neutralized after reaction)
In Example 7, the amount of PhG-30 added to the separable flask was 75.0 g, the amount of dimethylaminoethyl methacrylate in the monomer / initiator solution was 180.16 g, the amount of butyl methacrylate was 69.84 g, and the amount of PhG-30 was 270.7 g, the amount of V-65B was changed to 4.88 g, the amount of V-65B in the initiator solution dropped after completion of dropping of the monomer / initiator solution was changed to 3.25 g, and the amount of PhG was changed to 29.3 g. . Furthermore, DL-lactic acid was not added to the monomer / initiator solution, and finally 58.32 g was added after maintaining at around 80 ° C. for 2 hours. Otherwise in the same manner as in Example 7, a polymer PhG-30 solution was obtained. The Mw (water / ethanol = 7/3 system, polyethylene oxide equivalent) of this polymer was 16,600. The composition of this polymer analyzed by ¹ H-NMR was the same as the charged monomer composition.

  Table 4 summarizes the polymer compositions and neutralization conditions of Example 7 and Comparative Example 5 and the hues of the polymer solutions.

Claims (4)

A method for producing a polymer by polymerizing monomer components containing the following monomer (A) and monomer (B),
The polymerization is performed by a solution polymerization method using at least one selected from ethanol, 2-phenoxyethanol, and phenyltriglycol as a solvent,
Before or during the polymerization reaction, part or all of the monomer (A) is neutralized with a hydroxycarboxylic acid having a total carbon number of 1 to 22 and containing no aromatic ring.
A method for producing a polymer.
(A) an unsaturated bond-containing monomer having at least one amino group selected from primary to tertiary amino groups (B) an unsaturated bond containing a hydrophobic group and not having primary to tertiary amino groups (Meth) acrylic acid ester, (meth) acrylic acid ester, (meth) acrylamide, vinyl ester, vinyl ether and styrene, which are monomers having a linear, branched or cyclic alkyl group, alkenyl group, or aryl group having 1 to 22 carbon atoms At least one monomer selected from the group The method for producing a polymer according to claim 1, wherein the hydroxycarboxylic acid having 1 to 22 carbon atoms not containing an aromatic ring is a hydroxycarboxylic acid selected from glycolic acid, lactic acid, tartaric acid, malic acid, citric acid, and gluconic acid . The method for producing a polymer according to claim 1 or 2, wherein the amount of the hydroxycarboxylic acid having 1 to 22 carbon atoms not containing an aromatic ring is 0.1 to 1.5 equivalents relative to the amino group of the monomer (A). .   The monomer (A) is at least one monomer selected from (meth) acrylic acid esters having 1 to 3 primary amino groups, (meth) acrylamide, styrenes, and diallyl compounds. A method for producing the polymer.